Preparation of alkyl phenols



Reissues! Decsome PREPARATION OF ALKYL PHENOLS James A. Arvin, Homewnod, 111.. and James V.

Hunn, Avon Lake,

hlo.assignorsto ThesherwIn-Wiliiams Company, Cleveland. Ohio. a corporation of Ohio No Drawing. Original No. 2,415,069, dated February 4, 1947, Serial No. 428,408, January 12, 1942. Application for reheue January 10, 1048,

Serial No. 3,187

Claims.

The present invention relates to the manulecture 01 alkyl phenols, and in particular tertiary butyl phenol and tertiary octyl phenol. These respectively, are well known products of condensing phenol with isobutylene and diisobutylene. Buch condensations require a catalyst. Various catalysts have been proposed heretofore. These permit varying conditions for the condensation reaction, and in turn provide the alkyl phenols with varying amounts of impurities and varying yields.

It is an object of the present invention to produce alkyl phenols.

It is a special object of the invention to produce octyl and butyl phenols of such superior grade in the crude form that they may be used without any purification by distillation, in a condensatlon with formaldehyde to produce resins of superior quality for producing superior varnishes.

It is another object of the invention to use tetraphosphoric acid as the catalyst for condensing phenol and an olefin in a liquid phase reaction with or without a solid substrate.

It is a further object of the invention to use a solid substrate to improve the action of tetraphosphoric acid catalyst.

Other and ancillary objects and advantages of the invention will appear from the following description and explanation of the invention.

The present invention is directed to the use of catalysts and in particular to the use of tetraphosphoric acid as the catalyst. It also relates to the use of a secondary material or substrate, which adds to the eiilciency of tetraphosphoric acid as a catalyst. Buch secondary material is of the character known as surface active material, and it is particularly exemplified by acidactivated iuller's earth. However, it is not limited to acid-activated clays. Other materials are suitable such as bentonite, infusorial earth, kaolin, sand, powdered pumiw, and even powdered carborundum. These are characterized by being siliceous, or containing silicon or its oxide silica as such or as a silicate, and by high specific surface. It is believed that they absorb the tetraphosphoric acid to their surfaces to increase its eflectiveness. However, all materials having high specific surface are not suitable. For example, wood charcoal and animal charcoal have an opposite eilect and decrease the effectiveness of tetraphqsphorlc acid, while ignited alumina is but slightly less depressive. The efl'ective agents are mineral agents 0! high smciiic surface and Matter enclosed in heavy brackets I: 1 appears in the original patent but forms no part of this reissue specification: matter printed in italics indicates the additions made .by reissue 2 not organic agents, as the charcoal form oi carbon is considered to be.

According to the present invention the condensation is carried out using tetraphosphoric acid as a catalyst. Heretofore acids of phosphorus have been recommended, as for example by Ipatiefi in U. 8. Patent No. 2,046,900, which names hypo phosphorus, ortho phosphorus, pyro-phosphorus, hypo-Phosphoric, meta-phosphoric, pyro-phosphoric, and ortho-phosphoric acids. These vary in the yields which they give, but none oi them gives a yield as high as, nor properties as good as, what are obtained by using tetraphosphoric acid under similar conditions. Tetraphosphoric acid is an acid of phosphorus not heretofore considered as a catalyst, and not commonly known or available. It is described as a solid acid having the formula HsP-iOn melting at 34 (3., density 1.8886. (See Chemker Zeitung 1923, vol. 47, pa e 195, Ahstracted 17 C. A. 1929; and J. Russ Phys. Chem. Soc, 1921, vol. 53, I, p. 376-7, Abstracted 17 C. A. 3145.)

Where the secondary agent is the preferred acid-activated clay, the clay is one activated by an acid agent, such as hydrochloric acid, so that it is no doubt an acid agent having adsorbed acid on its surface. It is known in the art as a surface-catalyst when used alone. Various forms 01' this single catalyst are known for the condensation of oleflns with phenols, and are designated as acid-activated bleaching earth, tonsil, super-filtrol, etc. See U. S. Patent No. 2,091,565. We prefer the form known as "Top notch clay," an imported variety of fuller's earth, activated by acid, and available from L. A. Solomon 8; Co., 216 Pearl Street, New York city. However, because non-activated clays also act in a similar way in the present invention, acid-activated clay is not essential to the present invention, nor need it be considered as an essential catalyst in the present invention.

The value and utility of an alkyl phenol is reflected in the quality and properties of phenolaldehyde resins made from it, for use in varnishes. It is important to avoid color, and impurities, and to secure high yield. It is important in the varnish to avoid tackiness resulting from the resin. One advantage from the present invention is the fact that a crude alkyl phenol is obtainable which may be used in solution, as in mineral spirits, direct from its manufacture, without the crude alkyl phenol requiring a distillation to produce a product of purity suitable for resin manufacture. A purification by distillation results in loss or alkyl phenol over that available in the crude undistllled product. This loss may thus be avoided where it is permissible not to isolate the alkyl phenol. The undistilled phenol produced by the present invention produces directly a resin which makes a varnish tree from tackiness.

In the present invention, where the clay or the like is not used, the tetraphosphoric acid as a catalyst gives an octyl phenol formaldehyde resin which when used in a varnish gives films of a light yellow shade, and hence such resins are of more limited utility than the resins from the preferred procedures. when an activated earth is used alone as catalyst, a crude alkyl phenol is obtained, the resin of which has good color but is slightly slower in drying in a varnish, and yields are lower. Also the octyl phenol formed is known to be of lower grade. But when tetraphosphoric acid is used as catalyst in combination with a substrate excellent yields of almost water-white resins result having all the desired properties, and it is known that a high grade of octyl or butyl phenol is iormed. The substrate has in addition to its substrate function, a color-absorbing property, and the process is particularly conducted to exercise this function.

The crude alkyl phenol is formed by condensation in the presence of the catalyst. Then to the end-mass of the condensation a solvent, such as mineral spirits, is added, the solvent preferably being one which may be used in a subsequent step of forming the resin. Then the mass is washed with hot water one or more times, the heat preventing solidification of the alkyl phenols. Where clay is used, it settles in the water layer and is removed with the water layer, into which any residue of tetraphosphoric acid is also removed from association with the alkyl phenol. An extra step may be employed to assure removal of any residual acid of phosphorus or organic ester therewith. to avoid or minimize the possibility of ultimately forming a poorlydrying or non-drying resin or varnish, such as adding calcium carbonate as later described. The solution of crude alkyl phenol in the solvent, such as mineral spirits, is then used in a well known way for condensation with formaldehyde to form resin.

EXAMPLE 1 The following ingredients are employed:

Parts by weight Phenol 470 Tetraphosphoric acid 50 Di-isobutylene 560 Mineral spirits (B. P. 2004300 F.) 360 Calcium carbonate 3 Water (except wash water) 580 Sodium bisulphite 16 The phenol and tetraphosphoric acid are heated to 160 F. Then the di-isobutylene is run in slowly during one hour with eflicient agitation. The batch is held at 155 F. for two hours. All the mineral spirits is added and the batch washed twice with water. Then 16 parts of the sodium bisulphite are added and the batch stirred to minutes at 150-160 F., and again washed with water. The calcium carbonate is added and stirred in at 150 F. for minutes. Then 500 parts of wash water are added, agitation stopped and calcium precipitate allowed to settle. The mineral spirit solution of crude octyl phenol is separated and filtered, as through cheese cloth 4 into a reaction vessel tor subsequent purification, or for direct use by condensation with formalin to form a resin.

EXAMPLE 2 Parts by weight Phenol (CsHsOH) 4'70 Di-isobutylene 1 560 Fuller's earth 52 Tetraphosphoric acid 5 Mineral spirits (B. P. 200-330 F.) 360 Water (except wash water) 580 l 5 moles.

The phenol, the fullers earth and the tetraphosphoric acid are heated to 160 F. with violent agitation in an inert atmosphere. While maintaining the temperature at -160 FL, diisobutylene is slowly added over a period of two hours. With temperature at 155-160 F. the mass is agitated for 15 to 20 minutes after completion of said addition. The mineral spirits and wash water are added and agitated for 15 minutes. The clay settles and the clay and water are separated from the supernatant solution. The solution is again washed with water and the nonaqueous solution recovered, being first filtered as by straining through cheese cloth.

EXAMPLE3 In Example 2 the tetraphosphoric acid is increased to 10 parts.

EXAMPLE4 In the procedures of Examples 2 and 3, the tetraphosphoric acid is more easily removed as a phosphate by adding 33 parts of precipitated chalk when the mineral spirits and water are added. The precipitated phosphate is withdrawn with the clay.

EXAMPLE 5 Parts by weight Phenol 4'70 Di-isobutylene 560 Tetraphosphoric acid i0 Top notch clay {i2 Mineral spirits (B. P. 200-330 F.) 360 Water 580 Sodium blsulphite 8 The phenol, clay and tetraphosphoric acid are mixed and heated with agitation, keeping the temperature as close as possible to F. The di-isobutylene is added during two'hours while maintaining this temperature. Then the mixture is held at this temperature from 10 to 15 minutes, when it is diluted with the mineral spirits. If necessary the mass is heated again to 160 F. and a solution of 8 grams of the sodium bisulphite dissolved in 1000 parts of water is added and allowed to exert its functions at 160 F. for 15 minutes. The clay and water layer are drawn 0i! and the mineral spirit solution is washed with water.

EXAMPLE6 In any 01' the preceding examples the solution of crude actyl phenol may be bleached. After the heating period following the introduction of the di-isobutylene, the mineral spirits is added along with 8 parts of sodium bisulphite in 1000 parts of water, and the liquid heated at 160 F. for 15 minutes to effect a bleaching action by the sulphur dioxide content of the sulphite. This represents the first water wash, and then a second is used where water alone is employed.

sales 5 was:

' Parts by weight Phenol (Cal-150K) 470 Fuller's earth 52 Tetraphosphoric acid l Di-isobutylene l 560 Mineral spirits (B. P. 200-330 F.) 360 Calcium carbonate 3 Water (not including wash water)---" 580 Sodium hydroxide (25%) solution 445 Formalin (38-40%) 030 Sodium bisulphlte 24 Electrolytic sulphuric acid 159-155 5 moles.

' 11.1 moles.

Electrolytic sulphuric acid as above given contains 93% sulfuric acid by weight. The phenol clay and tetraphosphoric acid are heated to 160 F. with etflcient agitation in a lead-lined vessel. Di-isobutylene is added during 2 to 29: hours holding the temperature at 160 F. Then agitation is continued for 20 minutes. Mineral spirits and 16 parts of the sodium bisulphite are added, and the agitation continued for from to 20 minutes. About 900 parts of wash water (not in the contents listed above) are added and stirred for 5 minutes. After settling, the water is drawn 011. Then the calcium carbonate is added at 150 F., and the mass stirred for 29 minutes. Then 500 parts additional wash water are added and residual calcium carbonate allowed to settle. The water and precipitate are drawn oil, and the warm solution of crude octyl phenol in the mineral spirits is filtered into a nickel-surfaced vessel, as by straining through cheese cloth.

The measured 580 parts of water, and the caustic soda solution are then added and the temperature again brought to 160 F. and maintained in the range from 160 F. to 1'75 F. with stirring while the formalin is added over 20 to 30 minutes. This heating is continued for an hour. Then the remaining 8 parts of bisulphite in solution form are added, followed by the sulphuric acid until slight acidity to Congo red is indicated. The water layer is discarded and the resin washed once with water (not in the list above) The resin is hardened by heating to 300 to 310 F. in about one hour, and holding at this temperature for from 15 to 20 minutes. Yield is 1100 to 1150 parts of rain.

In the foregoing examples all of the crude octyl phenol was converted directly to resin by condensation with formalin. Hence the yield of phenol was not determined. However, where the yields of resin were determined, all irom 470 parts of phenol (CaHsOH), they were as follows:

Parts of resin Example 2 an 1100 Example 7 1100 to 1150 In order to compare the efllciency of various secondary agents or substrates a set procedure recovering the phenol has been adopted as follows:

The phenol, iullers earth. and tetraphosphoric acid are heated to 160 1". with eihcient asltation, and the di-isobutylone is added gradually during a period oi three hours while the temperature is maintained at -100 1''. After all the di-isobutylene is in, the temperature is held at F. while stirring is continued for twenty minutes. The mineral spirits and sodium bisulflte are added and the mixture is agitated for ten minutes, whereupon 1000 parts of warm water are added and the mixture agitated vigorously for another ten minutes. The layers are allowed to separate and the lower aqueous layer is drawn oil and discarded. The calcium carbonate is added to the upper layer and vigorous agitation maintained for twenty minutes, followed by another wash with 1000 parts of warm water. The lower aqueous layer is carefully drawn on and the upper layer submitted to distillation in vacuo. A fore-run consisting of mineral spirits, traces of phenol and of water first dlstills, then the main fraction consisting of pure octyl phenol distills at 168-169 C. at 19 mm. pressure. The amount 0! pure product obtained equals 1220 parts by 7 weight, which represents a 95% yield. Sometimes it is necessary to wash the solution of octyl phenol in mineral spirits with a very dilute solution of a base, such as sodium carbonate, to remove the last traces of mineral acid prior to distillation. Octyl phenol decomposes when distilled in the presence of small amounts of acid. This is one reason why a high grade crude alkyl phenol, not requiring distillation. is most valuable for high yield of high grade resin, for making superior varnishes.

The experiments employing substrates other than fullers earth were carried out identically as above, except that the 57.5 parts of fullers earth was replaced by an equivalent weight of The substrates tested and the other substrate. percent yield of octyl phenol from each are:

Per cent Substrate yield of octyl phenol Powdered carborundum. 55 3 Wood charcoal 2. 9 Animal charm] Less than 1 Powdered pumicc 4e. 4 Aluminum oxide (ignited)- H. 5 Kaolin 70. 2 land 47, 2 lniueorial earth 85. 2 liientonite 84. 4

DISCUSSION In all or the examples above given, the reaction temperature for making octyl phenol is given near 160 F. for a reason. Experience has shown that the procedures which give the purest octyl phenol shown solidification oi the contents at below this temperature. But where the particular process gives a less pure octyl phenol the solidiiioation occurs at a lower temperature. Therefore, in expectation of purer products, the procass is operated to avoid solidification in process. It has also been found that where the reaction occurs at higher temperatures, the crude octyl phenol is less pure, as indicated by a lower melting point when tested. Apparently higher temperatures accelerate or induce undesirable side reactiom. Poorer resins result from the lower melting crude octyl phenols. However, it is not necessary to keep the reaction always at 160 F. Temperatures from 100' 1". to F. are permitted, but where the purer alkyl phenols are obtained,

lower initial reaction temperatures may be raised sales to 160" l". as solidification begins to occur. This preferred procedure is suitable for the tetraphosphoric acid catalyst with or without a substrate. But where the acid-activated clay is used with the tetraphosphoric acid the product is so pure when the process is carried out at or below 160 F., that the'reaction product will solidify near the end of the reaction at temperatures not much below 160 F. Therefore, it is desirable to finish the reaction at 160 F., and then upon cooling the solution, its liquidity, or degree of mushiness from partial solidification gives a very good indication of the purity of the octyl phenol upon which can be predicated the probable purity of the resin when properly made by a tested procedure.

This is quite well illustrated by variations of Example 7 in which other acids of phosphorus have been substituted for the preferred tetraphosphoric acid. The efiect of the particular acid has been observed in various places in the process through to varnishes made from the resins. In the following table the vertical columns denote as follows:

A-acid used B-amount of acid C-heat of reaction D-solidity oi the octyl phenol solution at 75 F.

E-yield of resin F-color of resin (It-drying time of varnish coat to a dust-free (dustable) surface, in minutes.

Hcharacter of varnish coat after drying over ni ht.

Jcolor of varnish Control refers to a reference resin made from a purified butyl phenol, merely for the purpose of comparison. The control resin has a lower aldehyde content, but when the aldehyde contents of the control and of the resin from Example '7 are the same, the drying-to-dust-free times are the same.

drawn oil, and the washing operation repeated' once with subsequent water separation.

The chalk was added and the mixture stirred ten minutes at 150-160 F., agitation was halted and 1000 parts of hot water added. The lower water layer was carefully drawn off and the upper phenol-naphtha layer filtered through cloth. The phenol-naphtha layer amounted to 874 parts by weight.

For the purposes of resin manufacture, the butyl phenol is not isolated. In order to determine the actual yield of butyl phenol, a 250 part aliquot of the phenol-naphtha mixture was diluted with C. P. benzene, washed once with flve percent sodium carbonate solution, then once with distilled water. The solvents were distilled under diminished pressure, leaving the crude butyl phenol which was distilled in vacuo. After a slight fore-run of colorless oil which would not solidify, there was obtained 196 parts of practically pure p-ter-butyl phenol, B. P. 122-123 C. at 15 mm., 236-238 C. at atmospheric pressure. This is equivalent to 684 parts of pure product in the original 874 parts of crude, or a yield of 91.3%.

EXAMPLE 10 The materials used in Example 9, omitting the fuller's earth and any other substrate, are employed in the same way. The reaction is more retarded where the substrate is absent. and the quick rise in temperature noted in Example 9 was absent. After 2.5 hours of adding 286 parts of isobutylene, 272 parts of it were absorbed by TABLE A B O D E F G H 1 Phosphorus 10 Strong Hard 1, 071 Light.-. 131 Hard with trace of tack Light. Cube-phosphoric... 15 d .do l, do 116 a Do. Mata-phosphoric 10 Moderate Liquid 91 Dark Overl75 Tack Do. Pyro-phosphoric.. 10 Strong ard 1,118 Light.-." 131 Hard with trace oi tack. Do. Tetra-phosphoric 10 ..do.. d0.- ,1 do. 116 Hard Do. Control r 136 do BUTYL PHENOL When the condensation is carried out with isobutylene, tertiary butyl phenol results. The same principles are involved, and care is taken to avoid solidification of butyl phenol in process of production. This solidifies at a higher temperature than the octyl phenol, and therefore slightly higher temperatures are required. A longer time also has been used.

The phenol, fullers earth, and tetraphosphoric acid were heated to 170 F. and the introduction of isobutylene commenced. The temperature inithe reaction mass. The distilled and recovered tertiary butyl phenol showed a yield of 62.5%.

It is to be appreciated that the invention is not limited to and by the specific examples herein given to illustrate the nature or the invention. Numerous changes and modifications are contemplated as falling within the scope of the appended claims.

The present application is a continuation in part of our earlier application Serial No. 211,568, filed June 3, 1938.

We claim:

1. The process of making aikyl phenols which comprises condensing substantially equimolecular proportions of phenol and of a hydrocarbon of the group consisting of isobutylene and di-isobutylene in the presence of tetraphosphoric acid as a catalyst under substantially anhydrous conditions and in the presence of an acid-activated siliceous material having high specific surface at a temperature in the range from F. to F. selected to avoid solidification in the reacting mass, while employing tetraphosphoric acid in cares an amount in the range from i to 10 weight units for each molecular weight unit of the phenol, mixing the mass with water and a volatile waterlmrniscible organic solvent for octyl phenol, whereby to form an aqueous layer containing the catalyst and a separable solvent layer containing a product of such condensation in the form of an alkyl phenol of the group consisting of butyl phenol in the case of lsobutylene and octyl phenol in the case of di-isobutylene, and isolating the solvent layer as -a source of alkyl phenol.

2. The process of making octyl phenol which comprises condensing substantially equimolecular proportions of di-isobutylene and phenol in the presence of tetraphosphorlc acid as a catalyst under substantially anhydrous conditions, and in v the presence of an acid-activated siliceous material having high specific surface at a temperature in the range from 100' F. to 180 1'. selected to avoid solidification in the reacting mass, while employing tetraphosphoric acid in an amount in the range from 1 to 10 weight units for each molecular weight unit of the phenol, mixing the mass with water and a volatile waterimmiscible organic solvent for octyl phenol. whereby to form an aqueous layer containing the catalyst and a separable solvent layer containing octyl phenol, and isolating the solvent layer as a source of octyl phenol.

3. The process of making butyl phenol which comprises condensing substantially equi-molec-- ular proportions of di-lsobutylene and phenol in the presence of tetraphosphoric acid as a catalyst under substantially anhydrous conditions, and in the presence of an acid-activated siliceous material having high specific surface at a temperature in the range from 100 to 185 F. selected to avoid solidification in the reacting mass, while employing tetraphosphoric acid in an amount in the range from 1 to 10 weight units for each molecular weight unit of the phenol, mixing the mass with water and avolatile waterimmiscible organic solvent for butyl phenol, whereby to form an aqueous layer containing the catalyst and a separable solvent layer containing hutyl phenol, and isolating the solvent layer as a source of butyl phenol.

4. In a process or making an alkyl phenol the steps which comprise heating phenol with an acid activated fullers earth and tetraphosphoric acid, adding a hydrocarbon selected from the group consisting of lsobutylene and di-isobutylene while holding the temperature within the range of 100 F. to 185 F., and subsequently separating the resultant allryl phenol from the reaction mass, said reaction being effected under substantially anhydrous conditions.

5. In a process of making butyi phenol the steps which comprise heating together phenol and tetraphosphoric acid in the presence of an acid activated fuller's earth, and adding lsobutylene to the resultant heated mixture in approximately equlmoiecular proportions of lsobutylene to phe- 1101, while holding the temperature during the addition of the lsobutylene suillciently high to avoid solidification and within the range of about 100 F. to about 185 F., said reaction being eilected under substantially anhydrous conditions.

6. The process of making alkyl phenols which comprises condensing substantially equimolecular proportions of phenol and of a hydrocarbon of the group consisting of lsobutylene and di-isobutylene in the presence of tetraphosphoric acid I.

as a catalyst under substantially anhydrous conditions and in the presence of an acid-activated siliceous material having high specific surface at a temperature in the range from F. to 185' F. selected to avoid solidification in the reacting mass, mixing the mass with water and a volatile water-immiscible organic solvent for octyl phenol, whereby to iorm an aqueous layer containing the catalyst and a separable solvent layer containing a product of such condensation in the form or an alkyl phenol of the group consisting of butyl phenol in the case of lsobutylene and octyi phenol in the case of iii-lsobutylene, and isolating the solvent layer as a source of alkyl phenol.

'l. The process of making octyl phenol which comprises condensing substantially equlmolecular proportions of til-lsobutylene and phenol in the presence of tetraphosphorle acid as a catalyst under substantially anhydrous conditions and in the presence of an acid-activated siliceous material having high specific surface at a temperature in the range from 100 1". to F. selected to avoid solidification in the reacting mass, mix-' ing the mass with water and a volatile waterimmiscible organic solvent for octyl phenol, whereby to form an aqueous layer containing the catalyst and a separable solvent layer containing octyl phenol, and isolating the solvent layer as a source of octyl phenol.

8. The process of making butyl phenol which comprises condensing substantially equimolecular proportions of [dilisobutylene and phenol in the presence of tetraphosphoric acid as a catalyst under substantially anhydrous conditions and in the presence of an acid-activated siliceous material having high speciflc surface at a temperature in the range from 100 F. to 1". selected to avoid solidification in the reacting mass, mixing the mass with water and a volatile water-immiscible organic solvent for butyl phenol, whereby to form an aqueous layer containing the catalyst and a separable solvent layer containing butyl phenol, and isolating the solvent layer asa source of butyl phenol.

9. A process for the alleviation of a phenol with an oleflne which comprises subaectino a phenol to the action of a branched chain oleflne in the presence of a catalytic amount of ietraphosphorie acid at alkul phenol forming temperatures not exceeding about 185 degrees F.

10. An improved process for the alleviation of a mono-hydric phenol with oleflnes comprising treating a mono-hudric phenol in the presence of a catalytic amount of tetraphosphoric acid with a branched chain oleflne at alkzrl phenol forming temperatures not exceeding about 185 degrees F.

11. An improved process for the alleviation of mono-hpdric phenols with oleflnes comprising treating a mixture consisting essentially of at least one mono-hudric phenol and tetraphosphoric acid in an amount corresponding to at least about 2% by weight of said mono-hydric phenol with a branched chain olefine at an alkul phenol forming temperature not exceeding about 70 degrees 0., and separating the alkplated monohydric phenol reaction products from the tetraphosphoric acid.

12. An improved process for the alleviation of mono-hydric phenols with olefines comprising treating a mixture consisting essentially of at least one mono-hpdric phenol and tetraphosphoric acid in an amount corresponding to 5 to 10% 1! weight of said mono-hudric phenol with 11 a branched chain olefine at an allcgl phenol Iorming temperature not exceeding about 70 degrees 0. and separating the alleviated mono-hpdric phenol reaction products from the tetraphosphoric acid catalyst. 5

13. An improved process for the alkglation oi mono-hpdric phenols with a branched chain ole-t jlne comprising dissolving tetraphotphoric acid in catalytic amounts in mono-hpdric phenol and treatingthis solution at an alley! phenol forming l0 temperature not exceeding about 70 degrees C. with a branched chain oleflne.

14. An improved process for the alleviation of mono-hydric phenols with olefines comprising treating a phenol in the presence 0! a catalytic 1 amount of tetraphosphoric acid and as a sub- 12 stra'te an acid activated siliceous material having a high specific lurlace with a branched chain olefine containing at an allwl phenol forming temperature not exceeding 185 degrees I.

15. A process lor the alleviation of a phenol with a branched chain oleflne which comprises subjecting a phenol .to the action of a branched chain olenne in the presence of a catalytic amount of tetraphospltoric acid and an acid activated fullers earth at alkgl phenol forming temperatures not exceeding about 185 degrees F.

JAMES A. ARVIN. JAMES V. BURN.

No references cited. v

Certificate of Correction Reissue No. 23,183 December 20, 1949 JAMES A ARV'IN ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 67, for "acty read ootyl and that the said Letters Patent should be read with this correction therein that the some may conform to the record of the case in the Patent Oflioe.

Signed and sealed this 25th day of April, A. D. 1950.

THOMAS F. MURPHY,

Am'atmt dommiaaionar of Paton. 

